Strong CH…O Interactions in the Second Coordination Sphere of 1,10-Phenanthroline Complexes with Water.

Although CH…O hydrogen bonds are generally very weak, here investigated CH…O interactions of coordinated 1,10-phenanthroline (phen) are very frequent and quite strong. In the crystal structures from the Cambridge Structural Database, 8344 CH…O interactions between coordinated phen and water molecule in the second coordination sphere were found. We calculated all possible types of CH…O interaction energies at DLPNO-CCSDT/CBS level for non-coordinated and coordinated phen with a water molecule. The data for non-coordinated phen exhibited the weakest interactions, from -2.09 to -2.94 kcal/mol. Upon coordination of phen, interactions become stronger. In octahedral cobalt(II) complexes, interaction energies are from -3.37 to -4.35 kcal/mol. With the decrease in the complex coordination number, interaction energies become stronger, the strongest are for square planar palladium(II) complexes from -3.91 to -4.94 kcal/mol. There is a linear correlation between interaction energies and electrostatic potential values at the interacting hydrogen atom, with a correlation coefficient of 0.97. For all studied systems, the weakest is always a linear interaction, and the strongest is a bifurcated interaction. The strongest calculated CH…O interactions of coordinated phen with water in the second coordination sphere (-4.94 kcal/mol) are as strong as the hydrogen bond between two water molecules (-5.0 kcal/mol).